JPS62119545A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain a sharp transferred image by forming a photosensitive layer containing one or more specified p-cyclophane compounds on a conductive substrate. CONSTITUTION:The photosensitive layer formed on the conductive substrate 1 contains as an effective component at least one of paracyclophane compounds represented by formula I in which each of R1 and R2 is H, alkyl, alkoxy, or halogen, and each may be same or different. An electrostatic charge generating layer 5 composed essentially of a charge generating material 3 and a charge transfer layer 4 containing the paracyclophane compound are laminated on the conductive substrate 1 to form the photosensitive layer 2''. In this photosensitive body, light transmitted through the charge transfer layer 4 arrives at the charge generating layer 5 to generate charge carriers in this region, and the layer 4 undergoes injection of the carriers, and participates in transfer of them, thus permitting photodecay necessary for generation of the charge carriers to be executed by the charge generating material 3 and transfer of the charge carriers to be executed in the layer 4, and therefore, a sharp transferred image to be obtained.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a photoreceptor used in electrophotography,
Specifically, the present invention relates to an electrophotographic photoreceptor containing a specific valacyclophane compound in the photoreceptor.

[Conventional technology]

Single-child photography has been widely known as one of the image forming methods. ``Electrophotography'' generally refers to a photoconductive photoreceptor that is first charged in a dark place, for example, by corona discharge, and then imagewise exposed to selectively dissipate the charge only in the exposed areas to create an electrostatic latent image. In this method, an image is formed by developing and visualizing the latent image portion of the image using electrostatic fine particles (toner) Lc composed of a coloring material such as a dye or pigment and a binder such as a polymeric substance.

The basic characteristics required of a photoreceptor used in such electrophotography are (1) ability to be charged to an appropriate potential in a dark place, (2) less dissipation of charge in a dark place, (5) Examples include scales that quickly dissipate charge when irradiated with light.

Light guide used in the electrophotographic method 1! Inorganic materials such as selenium, cadmium sulfide, and zinc oxide are examples of organic materials, but while each of these conventional inorganic materials has many advantages, they also have various drawbacks and are not always satisfactory. Ta. For example, selenium, which is currently widely used, has the above (1) to (3).
The conditions satisfy the optical spectrum, but the manufacturing conditions are difficult and the manufacturing cost is high. Furthermore, 1: Since there is no IJ' bending, it is not only difficult to process it into a belt shape, but it is also sensitive to heat and mechanical shock, so it requires great care when handling. There is also. Cadmium sulfide and zinc oxide are also used as photoreceptors by dispersing them in resin binders, but these photoreceptors are inferior in mechanical properties such as smoothness, hardness, tensile strength, and abrasion resistance. It cannot be used repeatedly as it is.

In recent years, electrophotographic photoreceptors using various photoconductive organic materials have been proposed to eliminate the drawbacks of these inorganic materials.
Some are in practical use. For example, a photoreceptor (U.S.% fF No. 5 54
842 Aro7 Photoreceptor sensitized with pyrylium salt color complex (
% published in Japanese Patent Publication No. 48-25658), a photoreceptor whose main component is M machine diverticulum (described in Japanese Patent Application Laid-open No. 47-37543), and a photoreceptor whose main component is a eutectic complex consisting of a dye and a resin. photoreceptor (described in %Kaishi No. 47-10735).

[Problems to be solved by the present invention]

These photoreceptors have excellent % properties and are considered to be relatively valuable for photoreceptor use, but when considering the above-mentioned characteristics required for electrophotographic photoreceptors,
It's not completely satisfying.

In general, the characteristics of photoreceptors vary depending on the purpose or manufacturing method, but they largely depend on the photoconductive material used, so they are sufficiently satisfactory as photoreceptors for electrophotography. There is a strong need for photoconductive materials with these properties.

[Means for solving problems]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photoreceptor that can eliminate the various drawbacks of the conventional photoreceptor mentioned above and fully satisfy the conditions required in electrophotography. The object of the present invention is to provide a suitable photoconductive material. Another object of the present invention is to provide an electrophotographic photoreceptor that is easy to manufacture, relatively inexpensive, and has excellent durability.

Therefore, the electrophotographic photoreceptor of the present invention is characterized in that a photosensitive layer containing at least one valacyclophane compound represented by the following general formula (1) as an active ingredient is provided on a conductive support.

[In the formula, R1 and R2 represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and may be the same or different]
) has been shown to work effectively as a photoconductive substance for electrophotographic photoreceptors.

Furthermore, as will be clear from the description below, the noguracyclophane compound can be combined with the following materials:
It has also been discovered that it is possible to create a photoreceptor with unexpected effects. The present invention was completed based on these findings.

That is, the present invention provides an electrophotographic photoreceptor in which a photosensitive layer is provided on a conductive support.
) is characterized by containing a valacyclophane compound represented by:

The present invention will be explained in detail below with reference to the drawings. Figures 1 to 5 are cross-sectional views of three typical examples of the photoreceptor according to the present invention, where 1 is the conductive support, 2, 2' and 2'' are the photosensitive nodes. , 3 represents a charge generation material, 4 represents a charge transport medium or charge transport layer, and 5 represents a charge generation layer.

The nozoracyclophane compound represented by the general formula (1) used in the present invention has the following general formula +tn: [wherein,
Yij-P-1(5)sZ-Ctatel, ? triphenylphosphonium group or -PO (OR
) 2 (wherein R represents a lower alkyl group) is a dialkyl phosphorous acid group] and a paracyclo7an derivative 4 body represented by the following, and the general formula [phase]: [wherein, R1 and R2 represents a water atom, an alkyl group, an alkoxy group, or a halogen atom, and R1 and R2 may be the same or different. I can do it.

Specific examples of the valacyclophane compound represented by the general formula (1) thus obtained are illustrated in Table 1.

The substitution positions are as shown in formula (IV).

Table 1 1-I H1( 1-24-OJ　H 1-35-0Hs　H 1-42-0HB H Compound A R4R2 1-54-0H54-0Hy.

1-6 3-0H53-01 (31-74-0
0H5H l-6,5-00J l( j -92-00H3H l -'1 0 4-00f i3
4-00H31-11' 3-001
13 3-OC1151-12,, 4-02H5H i -134-0021 (5H l -144-O6H 1-i5 5-01 Hl-162-
Ol H l -174'-Ol 4-Oll-184-
00H54-0H5- 1-194-00H5, 4-02H5 1-205-Ol 5-OL l -214-024-cn3 The photoreceptor of the present invention contains one or more of the above valacyclophane compounds. Depending on the application of these valacyclophane compounds, they can be used as shown in FIG. 1, FIG. 2, or FIG. 6.

The photoreceptor shown in FIG. 1 has a photosensitive layer 2 comprising a valacyclophane compound, a sensitizing dye, and a binder (binder resin) on a conductive support 1. The photoreceptor shown in FIG. The zoracyclophane compound here acts as a photoconductive substance, and the generation and transfer of charge carriers necessary for light attenuation take place via the valacyclophane compound. However, since the Noracyclophane compound has almost no absorption in the QJ viewing region of light, it is necessary to use a sensitizing dye that has absorption in the visible region for the purpose of forming an image with visible light. It is necessary to add sensitization.

The photoreceptor shown in FIG. 2 is provided with a photosensitive layer 2' on a conductive support 1, in which a charge generator "X5" is dispersed in a charge transport medium 4 made of a valacyclophane compound and a binder. Here, the paracyclo7an compound is used as a charge transport medium 4 along with a binder (or a binder and a plasticizer).
, while the charge generating substance 3 (charge generator 'X', such as an inorganic or organic pigment) generates charge carriers.

In this case, the charge transport medium 4 is mainly responsible for receiving charge carriers generated by the charge generating substance 3 and transporting them. In this photoreceptor, the basic condition is that the absorption wavelength regions of the charge generating substance 3 and the valacyclophane compound are not opposite to each other mainly in the visible region. This is because in order to efficiently generate charge carriers in the charge generating substance 'X3, it is necessary for e( to transmit light to the surface of the charge generating substance.

The valacyclophane compound represented by the general formula (I) has almost no absorption in the visible region, and generally absorbs light in the visible region, and when combined with a charge generating substance 3 that generates charge carriers, particularly effectively transports charges. The percentage that works as a substance
It is a sign.

The photoreceptor in FIG. 3 has a photosensitive layer 2'' consisting of a conductive support 1, a charge generation layer 5 mainly containing a charge generation substance 3, and a charge transport layer 4 containing a valacyclophane compound. In this photoreceptor, light transmitted through the charge transport layer 4 reaches the charge generation no. 5, and charge carriers are generated in that region. The generation of charge carriers necessary for optical attenuation is carried out by charge generation substance 3, and the charge carrier transport is carried out by charge transport no. ).This mechanism is similar to that described for the photoreceptor shown in FIG.

To actually produce the photoreceptor of the present invention, in the case of the photoreceptor shown in FIG. A photosensitive layer 2 may be formed by applying a liquid containing an infectious agent (preparing a liquid containing an infectious agent) onto a conductive support 1 and drying it.

The thickness of the photosensitive layer 2 is 5 to 50 μm, preferably 5 to 20 μm.
m is appropriate. The violet content of the valacyclophane compound in the photosensitive layer 2 is 60 to 70% by weight, preferably about 50% by weight, and the proportion of the sensitizing agent in the photosensitive layer 2 is 0.1% by weight.
~53 ttf%, preferably 0.5-3% by weight.

As sensitizers, triarylumecone dyes such as brilliant green, Victoria blue B1 methyl violet, crystal violet, acid violet 6B, rhodamine B10-damine 6G.

Rotamin G Extra, Eosin S1 Erythrosin,
Rose Bengal, xanthine dyes such as fluorescein, thiazine dyes such as methylene blue, cyanine dyes such as cyanine, 2,6-diphenyl-4-(N,
N-dimethylaminophenyl) thiapyrylium verchlorate, benzopyrylium salt (Japanese Patent Publication No. 48-25658
Examples include biryllium dyes such as those described in Japanese Patent Publication No. Note that these sensitizing agents may be used alone or in combination of two or more.

In addition, in order to produce the photoreceptor shown in FIG. 2, fine particles of the charge generator 'R3 are dispersed in a solution containing one or more valacyclophane compounds and a binder, and these particles are made conductive. The photosensitive layer 2' may be formed by coating the photosensitive layer 1 on the photosensitive support 1 and drying it.

The thickness of the photosensitive layer 2' is 6 to 50 μm, preferably 5 to 20 μm.
μm is appropriate. The amount of the valacyclophane compound in the photosensitive layer 2' is 10 to 95% by weight, preferably 30 to 95% by weight.
The violet content of the charge generating substance 3 in the photosensitive layer 2' is 0.1 to 50% by weight, preferably 1 to 50% by weight.
The cliff amount is 20%. Examples of the charge generating substance 6 include inorganic pigments such as selenium, selenium-tellurium cadmium sulfide, cadmium-selenium sulfide, and α-silicon; examples of organic pigments include C.I. Pigment Blue 25 (color index 0 2118'0) and C.I. Pigment Red 41 (0/21200), C.I. Acid Red 52 (0/45100), C.I. Basic Red 3 (0/45210), azo pigments with a carbazole skeleton (distributed in JP-A-53-95033, Distyryl Azo pigment with benzene skeleton (% opening/closing 53-1
33445), azo pigments having a triphenylamine skeleton (described in JP-A-55-132347), azo pigments having a dibenzothiophene skeleton (described in JP-A-54-21728), oxadi Azo pigments having an azole skeleton (distributed in JP-A-54-12742), azo pigments having a fluorenone skeleton (distributed in JP-A-54-12742),
4-22834), an azo pigment having a bisstilbene skeleton (described in JP-A-54-17733), an azo pigment having a distyryl oxadiazole skeleton (described in %Opening and Closing No. 54-2129) Azo pigments having a distyrylcarbazole skeleton (Japanese Patent Application Laid-Open No. 1496-1986)
Azo pigments such as C.I. Pigment Blue 16CO F.4100); indigo pigments such as C.I. But Brown 5 (A.F. 3410) and C.I. Pat Dyes (O.F. 3030); , Argo Scarlet B (Bayer a [L Indance Scarlet R (manufactured by Bayer)
Examples include perylene pigments such as. Note that these charge generating substances may be used alone or in combination with 241i1 or more.

Furthermore, in order to fabricate the photoreceptor shown in FIG. 3, the 'α charge-generating material is vacuum-deposited on the conductive support 1, or fine particles 5 of the charge-generating material are deposited in a suitable form with a binder dissolved therein if necessary. By applying a dispersion in a suitable bath medium and drying it,
Furthermore, if necessary, surface finishing and film thickness adjustment are performed by a method such as puff polishing to form a charge generation layer 5, and a bath containing 1a or two or more valacyclophane compounds and a binder is applied thereon. The charge transport layer 4 may be formed by spreading the liquid on a cloth and drying it. The charge generating material 3 used to form the charge generating layer 5 here is the same as that used in the description of the photosensitive material 2'.

The thickness of the charge generation layer 5 is 5 μm or more, preferably 2 μm.
The appropriate thickness of the charge transport layer 4 is 6 to 50 μm, preferably 5 to 20 μm. If the charge generation layer 5 is of the type in which charge generation particles 5 are dispersed in a binder, the charge generation layer 5 of charge generation particles 6 is
The proportion is 10 to 95% by weight, preferably 50 to 9% by weight.
0% by weight 8 fakes. Further, the amount of the valacyclophane compound in the charge transport layer 4 is 10 to 95% by weight, preferably 60 to 90% by weight.

In the production of any of these photoreceptors, the conductive support 1 is made of a metal plate made of aluminum or gold foil, a plastic film coated with metal such as aluminum, or paper subjected to conductive treatment. used. In addition, as a binder, combinations of materials such as polyamide, polyurethane, polyester, epoxy resin, polyketone, and polycarbonate, and vinyl polymers such as polyvinyl ketone, polystyrene, poly-N-vinylcarbazole, and polyacrylamide are used. However, any insulating and adhesive resin can be used. Mustichiyo υ142
agents are added to the binder; such "J'ffi agents include halogenated panfins, polychlorinated biphenyls,
Examples include dimethylnaphthalene and dibutyl phthalate.

Further, in the photoreceptor obtained by the above-mentioned process, an adhesive layer or barrier layer can be provided between the conductive support and the photosensitive layer, depending on the required VC. The materials used for these layers include polyamide, nitrocellulose, and albanium oxide, and the film thickness is preferably 1 μm or less.

In the case where the photoreceptor of the present invention is used for dispensing, the photoconductor surface is charged and exposed, and then the photoreceptor is exposed, and if necessary, the photoreceptor is transferred to paper or the like.

〔Effect of the invention〕

Since the photoreceptor of the present invention is constructed as described above, it has extremely excellent advantages as an electrophotographic photoreceptor, such as high sensitivity and flexibility.

Examples are shown below. In the examples, all parts are parts by weight.

Example 1 23.2 tons of triethyl phosphite and 20 tons of xylene were mixed and heated to 120 degrees centigrade to form a solution (4).

On the other hand, pseudogem-bis(bromomethyl)[:2
．． 2) Baraclofa: y (1'-J, Org, Oh
Em, J45, 3974 (1980) K.
The mixture was added to the bath solution (A) over 25 minutes. The solution thus obtained was reacted first at about 120°C for 2 hours and then at about 160°C for 1.4 hours. After the reaction was completed, xylene and excess triethyl phosphite were distilled off under reduced pressure, and the resulting orange-yellow liquid was further purified by column chromatography (silica gel, developing solvent: chloroform) to obtain a pale yellow liquid of &56t. Compound(
II) was obtained.

Compound (11) obtained in 1) (Y=PO(0021(5
)2) 1.49 f and compound position (R1-R2-H)
1.60F to N,N-dimethylformamide 25 m
It was commonly understood as t. This solution contains 0 potassium t-butoxide.
．． 98? was added and reacted at room temperature for about 25 hours. The reaction solution was poured into about 400 yards of water, and the resulting yellow precipitate was collected, washed with water, and dried to obtain a yellow powder of 130F. This powder was subjected to column chromatography twice (first time using silica gel, developing solvent: toluene, second time using silica gel, developing solvent dichlorohexane-toluene (4:1 volume ratio) mixed solvent) to produce a yellow resin. like thing (], 85
r (3 parts 8%) was obtained.

■) Preparation of photoreceptor Next, as a charge generation VI component, 876 parts of an azo face having a distyrylbenzene skeleton shown in Table 2, a 2% tetrahydrofuran solution of polyester resin (Vylon 200, manufactured by Toyobo Co., Ltd.) 1,260 parts of tetrahydrofuran and 3,700 parts of tetrahydrofuran were pulverized and mixed in a ball mill, and the resulting charge generation layer forming liquid was spread using a doctor grade onto the aluminum surface of a 24-volt support made of an aluminum-deposited polyester base. Approximately 1μ thick when dried
A charge generation layer of m was formed.

On the other hand, as a charge transport substance, the valacyclophane compound (AI-1) obtained in 11) 2 s1 polycarbonate resin (Panlite 1300, manufactured by Jojin Co., Ltd.) 2
After mixing and dissolving 16 parts of hydrogen and tetrahydrone to obtain a charge transport layer forming solution, this was applied onto the charge generating layer using a doctor blade, and dried at 80°C for 2 minutes and then at 105°C for 5 minutes. A charge transport layer having a thickness of about 20 μm was formed using the photoreceptor 1 to prepare a photoreceptor.

Examples 2 to 5 Photoreceptors 2 to 5 were prepared in exactly the same manner as in Example 1 except that the charge generating substance and the charge transporting substance (nosoracyclophane compound) were replaced with those shown in Table 2.

Charge Transport Example 6 On an aluminum plate with a thickness of about 300 μm, a charge generation layer was formed by vacuum evaporating selenium to a thickness of about 1 μm. Next, 2 parts of the Nora cyclophane compound No. 41-13, 3 parts of polyester resin (Polyester Base 49000 manufactured by DuPont) and 45 parts of tetrahydrofuran were mixed and dissolved to prepare a charge transport layer forming solution), and this was added to the above solution. The photoreceptor A6 of the present invention was prepared by coating the charge generation layer (selenium vapor deposited layer) using a doctor blade, air drying, and then drying under reduced pressure to form a charge transport layer with a thickness of about 14 μm. Obtained.

Example 7 A mixture of 1 part of Azoboro #+scissors having a trinodinylamine skeleton (same as those used in Example 6) and 158 parts of tetrahydrofuran was ground and mixed in a ball mill, and then AI-15 was added to this mixture. 12 parts of a valacyclophane compound, 18 parts of polyester M resin (Polyester Adhesif 49 manufactured by DuPont) were added, and the resulting photosensitive layer forming liquid was applied onto an aluminum-deposited polyester film using a doctor blade. A photoreceptor A7 of the present invention was obtained by coating the photoreceptor A7 by drying at 100° C. for 60 minutes to form a photosensitive layer with a particle size of about 15 μm.

The photoreceptor A1-7 thus produced was tested using a commercially available Seidenshashi paper tester (EIP428 manufactured by KK Kawajo Seisakusho).
After charging by performing a discharge of -6KV or +6KV (7):ffcl for 20 seconds using a tungsten lamp, leave it in a dark place for 20 seconds, measure the surface potential Vpo (volt) at that time, and then use a tungsten lamp. Irradiate light so that the irradiation area on the photoreceptor surface is 4.5 lux, and the surface potential is v.
Find the time (seconds) it takes for po to reach A, and calculate the exposure JtHl
'A (looks/second) was calculated. The results are shown in Table 3.

Further, each of the above-mentioned photoreceptors is charged using a commercially available electrophotographic JIc copying machine, and then light is irradiated through the original image to form an electrostatic latent image, which is developed using a dry developer and obtained. When the resulting image (toner image) was electrostatically transferred and fixed onto plain paper, a clear transferred image was obtained. The same clear transfer 1III is obtained when using a wet-type transfer agent as the transfer agent.
II violet was obtained.

Table 3 ? -15641,48 2-9861,23 3-10221,03 4-14062,07 5-12762,44 6-120814,10 7+936 3.80

[Brief explanation of drawings]

1, 2, and 3 are cross-sectional views enlarged in the thickness direction of an electrophotographic photoreceptor according to the present invention. 1... 4 is a support, 2e2'+2"... is not photosensitive, 3... is a charge generation vl: J fact, 4... is a charge transporting medium or a charge transporting layer, 5... is a charge generating layer .

Claims (1)

[Scope of Claims] An electrophotographic photoreceptor, characterized in that a photosensitive layer containing as an active ingredient at least one paracyclophane compound represented by the following general formula (I) is provided on a conductive support. . ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1 and R_2 are hydrogen atoms, alkyl groups,
Indicates an alkoxy group or a halogen atom, which may be the same or different]